CN115990501A - High-load single-atom catalyst and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a high-load single-atom catalyst and a preparation method and application thereof. The preparation method of the monoatomic catalyst provided by the invention comprises the following steps: s1, carrying out polycondensation reaction on melamine, cyanuric acid, L-alanine and phytic acid in the presence of a solvent to obtain a two-dimensional layered carrier, namely a 2D-polymer; s2, adding a precursor containing metal salt into the 2D-polymer, and stirring to obtain a polymer containing metal, namely M@2D-polymer; s3, freeze-drying the M@2D-polyme to obtain M@2D-polyme powder; s4, carrying out high-temperature treatment on the M@2D-polyme powder to obtain the monoatomic catalyst. The monoatomic catalyst obtained by the invention has a unique coordination structure, and the highest loading capacity can reach 35wt%. The preparation method of the single-atom catalyst has the advantages of good universality, low cost, high efficiency, simple operation, no need of acid etching, good reproducibility and controllable load, is suitable for transition metal and noble metal elements, and is more beneficial to large-scale production.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a high-loading single-atom catalyst, and a preparation method and application thereof.
Background
The single-atom catalysis establishes a bridge for homogeneous catalysis and heterogeneous catalysis, and becomes one of research hotspots in the current catalysis field. Compared with the traditional catalyst, the single-atom catalyst has obvious advantages, such as atom utilization rate can reach 100% theoretically; unsaturated metal sites exhibit better activity; the active site with definite structure is easier to reveal the catalytic process; high activity and selectivity, etc., which makes the catalyst have great prospect in industrial application.
However, the synthetic challenge of monoatomic catalysts is that the support is not effective in stabilizing the monoatoms because the metal atoms tend to aggregate into larger particles due to the sharp increase in surface free energy with decreasing particle diameter, and the more difficult the monodisperse atoms are to form with increasing loading. Therefore, the metal loading of many single-atom catalysts is relatively low, and the metal loading is generally 1wt% lower, which greatly limits the further application of the single-atom catalysts in industry.
Notably, some emerging synthetic strategies have been proposed to obtain such a unique class of supported monoatomic catalysts, such as Gu Meng et al synthesized 18wt% of Ir monoatoms on an O-defect-rich NiO support; hu Jinsong group of problems by adsorbing metal precursors on a carbon support of huge specific surface area, up to 12.1wt% of Co monoatoms are obtained; li Yadong group of subjects by means of polymer pyrolysis, fe monoatoms with a loading of ultra-high 30wt% were synthesized. Experimental results show that the synthesized high-loading monoatomic catalysts show excellent performance in the fields of electrocatalysis and the like.
However, the above synthetic strategies have limitations, such as being applicable to the synthesis of a specific single-atom catalyst, being less versatile, or having complicated preparation steps, low efficiency and high cost. Thus, developing a strategy for synthesizing high loading single-atom catalysts with versatility and low cost is currently a challenge.
Disclosure of Invention
The invention aims to provide a high-load single-atom catalyst, and a preparation method and application thereof. The obtained monoatomic catalyst has a unique coordination structure, and the highest loading capacity can reach 35wt%; the preparation method of the single-atom catalyst has the advantages of good universality, low cost, high efficiency, simple operation, no need of acid etching, good reproducibility and controllable load, is suitable for various transition metals, and is more beneficial to large-scale production.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for preparing a monoatomic catalyst, comprising the following steps:
s1, carrying out polycondensation reaction on melamine, cyanuric acid, L-alanine and phytic acid in the presence of a solvent to obtain a two-dimensional layered carrier, namely a 2D-polymer;
s2, adding a precursor containing metal salt into the 2D-polymer, and stirring to obtain a polymer containing metal, namely M@2D-polymer;
s3, freeze-drying the M@2D-polyme to obtain M@2D-polyme powder;
s4, carrying out high-temperature treatment on the M@2D-polyme powder to obtain the monoatomic catalyst.
In step S1, the solvent is at least one selected from deionized water, ethanol and acetone.
In the step S1, the mass-volume ratio of the melamine, the cyanuric acid, the L-alanine and the phytic acid is as follows: 1g: (0.5-4) g: (0.5-4) g: (100-500) μl; preferably 1g: (1-2) g: (1-2) g: (200-400) mu L.
In step S1, the conditions of the polycondensation reaction are: the temperature is 20-150deg.C, preferably 60-100deg.C, and the time is 1-1.5 hr, preferably 1 hr.
In the step S1, when the monoatoms are Fe, co, ni, cu or Zn, the solvent is deionized water; when the single atom is Ru or Ir, the solvent is ethanol.
In step S2, the metal salt is at least one selected from nitrate and hydrochloride corresponding to the metal element.
In the step S2, the mass ratio of the precursor containing the metal salt to the melamine is (0.001-0.5): 1, a step of; preferably (0.02-0.25): 1.
in step S2, the stirring causes the reaction system to be in a mud-like state.
In step S3, the conditions of the freeze-drying are as follows: under vacuum, the temperature is-5-20deg.C, preferably-10-15deg.C, and the time is 1-22 hr, preferably 20-22 hr.
In step S4, the conditions of the pyrolysis are: under inert gas atmosphere, the temperature is 500-800 ℃, preferably 700-800 ℃, the temperature rising rate is 2-10 ℃ for 1min, preferably 2-3 ℃ for 1min, and the time is 1-3h, preferably 1-2h.
The invention also provides the monoatomic catalyst obtained by the preparation method.
The monoatomic catalyst comprises the following components: a two-dimensional layered support and a single atom supported by the two-dimensional layered support;
the two-dimensional layered carrier is a nitrogen-oxygen doped carbon material.
The monoatomic group is a transition metal element, preferably at least one of Fe, co, ni, cu, zn, ru and Ir.
The structure of the monoatomic catalyst is M-N 3 O 1 Coordination, M is a single atom.
The loading of the single atoms is 0.1% -35%.
The pore diameter of the two-dimensional lamellar carrier is 0.1-100nm, and the specific surface area is 100-1000m 2 1g。
The invention also provides application of the single-atom catalyst in the fields of oxidation reaction, electrocatalysis, photoelectrocatalysis and hydrogenation catalysis.
The beneficial effects of the invention are as follows:
1. the series of monoatomic catalysts provided by the invention have a unique coordination structure, and the two-dimensional layered carrier has higher loading capacity which can reach 35wt% at most, so that the catalyst can show excellent catalytic performance when being used for homogeneous catalysis and heterogeneous catalysis reactions.
2. The copper monoatomic catalyst provided by the invention also has good circulation stability.
3. The preparation method provided by the invention can be used for rapidly preparing high-load single atoms in a large scale, is suitable for a series of transition metal elements, and has better universality.
4. The precursor used in the preparation method provided by the invention is low in cost and easy to obtain, the preparation process is simple and efficient, and certain large-scale production can be realized.
Drawings
FIG. 1 is a spherical aberration correcting high angle annular dark field scanning transmission electron microscope (HAADF-STEM) photograph of a copper monoatomic catalyst prepared in example 1 of the present invention.
FIG. 2 is a facial sweep plot of a copper monoatomic catalyst prepared in example 1 of the present invention.
FIG. 3 is a chart showing the K-edge EXAFS Fourier transform of Cu of the copper monoatomic catalyst prepared in example 1 of the present invention.
Fig. 4 shows the catalytic performance of the high-loading copper monoatomic catalyst prepared in example 1 of the present invention in the benzene oxidation reaction with hydrogen peroxide.
Fig. 5 shows stability of the high-loading copper monoatomic catalyst prepared in example 1 of the present invention in the reaction of hydrogen peroxide benzene oxide.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 preparation of high Supported Cu monoatomic catalyst
The preparation method comprises the following specific steps:
(1) Adding 2g of melamine, 2g of cyanuric acid, 2g L-alanine and 400 mu L of phytic acid into deionized water serving as a solvent, and carrying out in-situ polycondensation for 1h at the temperature of 100 ℃ to obtain a 2D-polymer;
(2) 270mg Cu (NO) 3 ) 2 ·4H 2 O, stirring to mud to obtain a Cu-containing 2D-polymer;
(3) Placing the obtained Cu-containing 2D-polyme in a vacuum dryer, freeze-drying at-10 ℃ for 22 hours, and removing the solvent to obtain Cu@2D-polyme powder;
(4) Under the protection of argon, the Cu@2D-polymer powder is heated to 700 ℃ at the rate of 1min at the temperature of 2 ℃, and naturally cooled after being kept for 2h, so that the Cu monoatomic catalyst with high load is obtained, and the load is 22wt%.
The spherical aberration correcting high angle annular dark field scanning transmission electron microscope (HAADF-STEM) photograph of the resulting copper monoatomic catalyst, as shown in fig. 1, demonstrates that copper exists in monoatomic form.
The resulting sweep profile of the copper monoatomic catalyst, as shown in fig. 2, demonstrates a uniform distribution of copper elements in the catalyst material. The pore diameter of the two-dimensional lamellar carrier is 3nm, and the specific surface area is 350m 2 1g。
The K-edge EXAFS Fourier transform spectrum of Cu of the obtained copper monoatomic catalyst is shown in FIG. 3, which proves that copper has Cu-N 3 O 1 Coordination structure.
Example 2 preparation of high Supported Fe monoatomic catalyst
The preparation method comprises the following specific steps:
(1) Adding 2g of melamine, 2g of cyanuric acid, 2g L-alanine and 400 mu L of phytic acid into deionized water, and carrying out in-situ polycondensation for 1h at 100 ℃ to obtain a 2D-polymer;
(2) 350mg Fe (NO) was added 3 ) 2 ·9H 2 O, stirring to mud to obtain Fe-containing 2D-polymer;
(3) Placing the 2D-polymer containing Fe in a vacuum dryer, freeze-drying at-10 ℃ for 22 hours, and removing the solvent to obtain Fe@2D-polymer powder;
(4) Under the protection of argon, the Fe@2D-polymer powder is heated to 700 ℃ at the rate of 1min at the temperature of 2 ℃, and is naturally cooled after being kept for 2h, so that the Fe monoatomic catalyst with high load is obtained, and the load is 21wt%.
Example 3 preparation of high Supported Co monatomic catalyst
The preparation method comprises the following specific steps:
(1) Adding 2g of melamine, 2g of cyanuric acid, 2g L-alanine and 400 mu L of phytic acid into deionized water, and carrying out in-situ polycondensation for 1h at 100 ℃ to obtain a 2D-polymer;
(2) 280mg Co (NO) was added 3 ) 2 ·6H 2 O, stirring to mud to obtain a Co-containing 2D-polymer;
(3) Placing the Co-containing 2D-polymer in a vacuum dryer, freeze-drying at-10 ℃ for 22 hours, and removing the solvent to obtain Co@2D-polymer powder;
(4) Under the protection of argon, the Co@2D-polymer powder is heated to 700 ℃ at the rate of 1min at the temperature of 2 ℃, and is naturally cooled after being kept for 2h, so that the Co monoatomic catalyst with high loading capacity is obtained, and the loading capacity is 21wt%.
Example 4 preparation of high Supported Ni monoatomic catalyst
The preparation method comprises the following specific steps:
(1) Adding 2g of melamine, 2g of cyanuric acid, 2g L-alanine and 200 mu L of phytic acid into deionized water, and carrying out in-situ polycondensation for 1h at 100 ℃ to obtain a 2D-polymer;
(2) 260mg Ni (NO) 3 ) 2 ·6H 2 O, stirring to mud to obtain a Ni-containing 2D-polymer;
(3) Placing the Ni-containing 2D-polymer in a vacuum dryer, freeze-drying at-10deg.C for 22h, and removing solvent to obtain Ni@2D-polymer powder;
(4) Under the protection of argon, heating Ni@2D-polymer powder to 700 ℃ at a rate of 1min at 2 ℃, and naturally cooling after keeping for 2h to obtain the Ni monoatomic catalyst with high loading, wherein the loading is 18wt%.
Example 5 preparation of high Supported Zn monoatomic catalyst
The preparation method comprises the following specific steps:
(1) Adding 2g of melamine, 2g of cyanuric acid, 2g L-alanine and 200 mu L of phytic acid into deionized water, and carrying out in-situ polycondensation for 1h at 100 ℃ to obtain a 2D-polymer;
(2) 450mg Zn (NO) was added 3 ) 2 ·6H 2 O, stirring to mud to obtain Zn-containing 2D-polymer;
(3) Placing the Zn-containing 2D-polymer in a vacuum dryer, freeze-drying at-10 ℃ for 22 hours, and removing the solvent to obtain Zn@2D-polymer powder;
(4) Under the protection of argon, heating Zn@2D-polymer powder to 700 ℃ at a rate of 1min at 2 ℃, and naturally cooling after keeping for 2h to obtain the Zn monoatomic catalyst with high load, wherein the load is 35wt%.
Example 6 preparation of high Supported Ru monoatomic catalyst
The preparation method comprises the following specific steps:
(1) Adding 2g of melamine, 2g of cyanuric acid, 2g L-alanine and 400 mu L of phytic acid into ethanol, and carrying out in-situ polycondensation at 60 ℃ for 1h to obtain a 2D-polymer;
(2) 90mg RuCl was added 3 Stirring to mud to obtain Ru-containing 2D-polymer;
(3) Placing the Ru-containing 2D-polymer in a vacuum dryer, freeze-drying at-10 ℃ for 22 hours, and removing the solvent to obtain Ru@2D-polymer powder;
(4) Under the protection of argon, ru@2D-polymer powder is heated to 700 ℃ at a rate of 1min at 2 ℃, and is naturally cooled after being kept for 2h, so that the Ru monoatomic catalyst with high load is obtained, and the load is 17wt%.
Example 7 preparation of high Ir Mono-atom catalyst loading
The preparation method comprises the following specific steps:
(1) Adding 2g of melamine, 2g of cyanuric acid, 2g L-alanine and 400 mu L of phytic acid into ethanol, and carrying out in-situ polycondensation at 60 ℃ for 1h to obtain a 2D-polymer;
(2) 50mg of IrCl was added 3 Stirring to mud to obtain Ir-containing 2D-polymer;
(3) Placing the Ir-containing 2D-polymer in a vacuum dryer, freeze-drying at-10 ℃ for 22 hours, and removing the solvent to obtain Ir@2D-polymer powder;
(4) Under the protection of argon, the Ir@2D-polymer powder is heated to 700 ℃ at the rate of 1min at the temperature of 2 ℃, and is naturally cooled after being kept for 2h, so that the Ir monoatomic catalyst with high load is obtained, and the load is 14 weight percent.
According to the embodiment 1-7, the nitrogen-oxygen doped two-dimensional layered carrier 2D-polymer prepared by in-situ polycondensation reaction of melamine, cyanuric acid, L-alanine and phytic acid can form a unique coordination structure with various single atoms (Fe, co, ni, cu, zn, ru and Ir), so that the nitrogen-oxygen doped two-dimensional layered carrier has better universality; meanwhile, through the coordination structure, the loading capacity of single atoms can be obviously improved to 35% at most, so that the prepared catalyst has better catalytic performance; in addition, the preparation raw materials in the method are cheap and easy to obtain, the preparation process is simple and efficient, and the loading capacity is controllable.
Application example 1
Taking the reaction of directly oxidizing benzene to prepare phenol by using the Cu monoatomic catalyst prepared in the embodiment 1 in a hydrogen peroxide one-step method as an example, the specific steps are as follows:
in a 25mL sealed glass reactor, 10mg of the Cu monoatomic catalyst prepared in example 1, 0.3mL of benzene and H were added 2 O 2 (30%) 0.4mL (benzene with H 2 O 2 The mol ratio of (1:1), acetonitrile 3.0mL, starting the reaction, and the reaction temperature is 60 ℃; after the reaction, the reaction product was filtered by a filter membrane, and ethyl acetate was added to extract the catalytic product.
The obtained catalytic product was analyzed by gas chromatography (GC, shimadzu, GC2010 plus) and gas mass spectrometry (GCMS, shimadzu, GCMS-QP 2010S) using n-tridecane as an internal standard.
The results were as follows:
the performance of the Cu monoatomic catalyst in the reaction of hydrogen peroxide and benzene is shown in figure 4, the conversion rate of benzene is 22 percent, the oxidation selectivity of benzene is 100 percent, and the corresponding hydrogen peroxide utilization rate is 22 percent during the reaction for 24 hours; when the reaction is carried out for 144 hours, the conversion rate of benzene is 50.1 percent, the oxidation selectivity of benzene is 99.5 percent, and the corresponding hydrogen peroxide utilization rate is 50.1 percent; from the above, the high-loading copper monoatomic catalyst provided by the invention can be used in the reaction of preparing phenol by directly oxidizing benzene with hydrogen peroxide in one-step method, and can obviously improve the oxidation selectivity of benzene and the utilization rate of hydrogen peroxide.
Application example 2
The phenol is prepared by using the recycled catalyst, and the specific steps are as follows:
(1) Regeneration of the catalyst:
separating the reaction liquid after 24 hours of reaction in application example 1, washing with ethyl acetate for three times, and vacuum drying at 60 ℃ for 2 hours to obtain a regenerated Cu monoatomic catalyst;
(2) 10mg of regenerated Cu single-atom catalyst, 0.3mL of benzene and H are added into a 25mL sealed glass reactor 2 O 2 (30%) 0.4mL (benzene with H 2 O 2 The molar ratio of (1:1), acetonitrile 3.0mL, starting the reaction at 60 ℃ for 24 hours; after the reaction, the reaction product was filtered by a filter membrane, and ethyl acetate was added to extract the catalytic product.
(3) The reaction liquid is separated again, washed three times by ethyl acetate, and dried in vacuum at 60 ℃ for 2 hours to obtain the regenerated Cu monoatomic catalyst which is recycled for 10 times.
Each obtained catalytic product was analyzed by gas chromatography (GC, shimadzu, GC2010 plus) and gas mass spectrometry (GCMS, shimadzu, GCMS-QP 2010S) using n-tridecane as an internal standard.
The stability of the circularly regenerated copper monoatomic catalyst in the reaction of hydrogen peroxide benzene oxide is shown in figure 5, and the catalyst is prepared by reacting benzene and H 2 O 2 Under the condition that the molar ratio of benzene is 1:1, the conversion rate of benzene is kept about 21 percent, the oxidation selectivity of benzene is kept about 99.7, and the corresponding hydrogen peroxide utilization rate is kept about 21 percent. Therefore, the high-load copper monoatomic catalyst provided by the invention can be recycled for more than 10 times, and has good recycling performance.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for preparing a monoatomic catalyst, comprising the following steps:
s1, carrying out polycondensation reaction on melamine, cyanuric acid, L-alanine and phytic acid in the presence of a solvent to obtain a two-dimensional layered carrier, namely a 2D-polymer;
s2, adding a precursor containing metal salt into the 2D-polymer, and stirring to obtain a polymer containing metal, namely M@2D-polymer;
s3, freeze-drying the M@2D-polyme to obtain M@2D-polyme powder;
s4, carrying out high-temperature treatment on the M@2D-polyme powder to obtain the monoatomic catalyst.
2. The method for preparing the monoatomic catalyst according to claim 1, wherein: in step S1, the solvent is at least one selected from deionized water, ethanol and acetone;
the mass volume ratio of the melamine to the cyanuric acid to the L-alanine to the phytic acid is as follows: 1g: (0.5-4) g: (0.5-4) g: (100-500) μl;
the conditions of the polycondensation reaction are as follows: the temperature is 20-150 ℃ and the time is 1-1.5h.
3. The method for producing a monoatomic catalyst according to claim 1 or 2, characterized in that: in the step S1, when the monoatoms are Fe, co, ni, cu or Zn, the solvent is deionized water;
when the single atom is Ru or Ir, the solvent is ethanol.
4. A process for the preparation of a monoatomic catalyst according to any one of claims 1 to 3, characterised in that: in step S2, the metal salt is at least one selected from nitrate and hydrochloride corresponding to the metal element;
the mass ratio of the precursor containing the metal salt to the melamine is (0.001-0.5): 1, a step of;
the stirring makes the reaction system mud-like.
5. The method for preparing a monoatomic catalyst according to any one of claims 1 to 4, wherein: in step S3, the conditions of the freeze-drying are as follows: under the vacuum condition, the temperature is between-5 and 20 ℃ and the time is between 1 and 22 hours.
6. The method for preparing a monoatomic catalyst according to any one of claims 1 to 5, wherein: in step S4, the conditions of the pyrolysis are: under the inert gas atmosphere, the temperature is 500-800 ℃, the temperature rising rate is 2-10 ℃ for 1min, and the time is 1-3h.
7. A monoatomic catalyst obtainable by the process of any one of claims 1 to 6.
8. The monoatomic catalyst of claim 7, wherein: the composition comprises the following components: a two-dimensional layered support and a single atom supported by the two-dimensional layered support;
the two-dimensional layered carrier is a nitrogen-oxygen doped carbon material;
the single atoms are transition metal and noble metal elements;
the structure of the monoatomic catalyst is M-N 3 O 1 Coordination, M is a single atom.
9. The monoatomic catalyst of claim 8, wherein: the loading amount of the single atoms is 0.1% -35%;
the pore diameter of the two-dimensional lamellar carrier is 0.1-100nm, and the specific surface area is 100-1000m 2 1g；
The monoatomic is at least one of Fe, co, ni, cu, zn, ru and Ir.
10. Use of the monoatomic catalyst according to any of claims 7 to 9 in oxidation, electrocatalysis, photoelectrocatalysis and hydrogenolysis applications.
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| CN116813449A (en) * | 2023-06-21 | 2023-09-29 | 中国科学院化学研究所 | Phosphorus coordinated iridium monoatomic catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde |
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| CN116813449A (en) * | 2023-06-21 | 2023-09-29 | 中国科学院化学研究所 | Phosphorus coordinated iridium monoatomic catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde |
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